TWI374127B - Process for isolation of an organic amine - Google Patents

Abstract

The invention relates to a process for the isolation of an organic amine from a composition comprising the organic amine and an acid, or a salt of the organic amine and the acid, wherein the process comprises steps wherein ammonia or hydrazine is added to the composition thereby forming a multi-phase system comprising an organic amine-rich phase and an acid-rich phase, the organic amine-rich phase and the acid-rich phase obtained in step (i) are separated, and the organic amine is isolated from the organic amine-rich phase.

Description

</ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; A method of separating the organic amine from the salt and acid composition. Background of the Invention Such a method is known from Japanese Patent Application No. JP-2004222569-A and JP-2004000114-A. In the known method of JP-2004000114-A, the organic amine is 1,5-pentanediamine, an organic amine also known as cadaverine, which is produced via a fermentation route in which L-isoamine is removed. The carboxylase allows for the action of the L-isoamine aqueous solution 'L-isoamine salt such as hydrochloride, sulfate, acetate, nitrate, or carbonate. The system containing cadaverine is an aqueous solution, and the acid in the salt is hydrochloric acid, sulfuric acid, acetic acid, nitric acid or carbonic acid. The cadaverine is said to be separated from the reaction solution by adding a strong base to the reaction solution, wherein the test is any of sodium hydroxide, potassium oxyhydroxide, and hydroxide feed, thereby raising the pH to 12-14, and subsequent extraction of cadaverine using a polar solvent such as strepamine, cyclohexanol, octinol, isobutanol, cyclohexanol, and gas imitation. A similar method is also described in jp_2〇〇4222569_a. Another method for separating cadaverine from a solution is described in JP-A-2004222569-A. In this alternative method, an organic solvent is added without using a strong test. The organic solvent is selected from the group consisting of alcohols, ketones and nitriles. The acid is hydrochloric acid or a second such as adipic acid, sebacic acid, succinic acid, or terephthalic acid. In this alternative method, the cadaverine is isolated as a salt with m. Patent No. 95148938, the inventor's book replaces this ι〇ι. 6 million cadaverine and the salt of cadaverine and dicarboxylic acid are said to be useful as raw materials for the manufacture of polyamine. A disadvantage of the first known method is that when a strong base or acid is excessive, a by-product is produced which is an aqueous solution containing a dissolved strong base salt which will result in significant loss of material in the process or, in addition, may require complex additional The treatment step separates the salt, acid and/or strong base from the aqueous solution. Further, when the method of JP-2004000114-A is reprocessed by the inventor, for example, using a gas-mold, it cannot be handled to a significant extent, or can not be handled at all. This alternative known method has the disadvantage that the amine impurities also formed in the fermentation process are easily incorporated into the cadaverine salt. When such an unpurified cadaverine disulfate is used in the manufacture of polyamines, the polymerization will result in a less desirable polyamine, or polymerization will not be feasible at all. On the other hand, it is extremely difficult (very few is not impossible) to use simple industrial methods to remove impurities from cadaverine ditoprosinate. C SUMMARY OF THE INVENTION J SUMMARY OF THE INVENTION The object of the present invention is to provide a method for separating the organic amine from a composition comprising an organic amine and an acid, or a salt comprising the organic amine, which method does not show the first known The method and the disadvantages of the known methods are either less or less disadvantageous. This item has been achieved using the method according to the invention, the method comprising the steps of: (1) adding ammonia or hydrazine to the composition, thereby forming a multiphase system comprising an organic amine rich phase and an acid rich phase, (ii) the organic-rich phase and the acid-rich phase obtained in the step (1) are separated by the use of the invention in the specification of 101. 6. 21, the patent application No. 95148938, and (iii) separating the organic phase from the organic-rich phase. amine. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 , FIG. 2 and FIG. 3 each show a method of integration into an organic amine, and a detailed description of a preferred embodiment of a device suitable for carrying out the single-off method of the present invention It has been unexpectedly found that the addition of sufficient ammonia or hydrazine to a composition comprising an organic amine and an acid, or a salt comprising an organic amine and an acid results in the formation of a multiphase system comprising an organic amine rich phase and an acid rich phase. As a result, if any I' is absent, the organic amine phase is lacking in acid content; if any amine is still present, the amine content of the acid rich phase is lowered. It has also surprisingly been found that organic amines have a better solubility in an ammonia-rich phase and/or a cerium-rich phase, or a better phase miscibility in an ammonia-rich phase and/or a cerium-rich phase; Or the salt of bismuth has a very low degree of fate or a very low compatibility in this phase, and can be added to a sufficient amount of ammonia and/or arable. An advantage of the method according to the invention is that in a single step, in other words, the addition of ammonia and/or hydrazine, the separation of the amine and the acid can be accomplished instead of using the two steps as in the first known method cited above. In addition, the organic amine can be separated from the ammonia-containing phase and/or the ruthenium-containing phase and any amine (4) in A by a simple means, and the advantage is that it is formed into a salt of the property. (4) Residual ammonia or split separation, and the remaining ammonia or the salt of the product is recovered and recovered for re-testing and separation. It is to be understood that the organic amine is here a compound substituted with at least one amine functional group covalently bonded to at least one carbon atom. The organic amine which can be used in the process according to the invention can be dissolved in any water-soluble or solubilizable salt form, and the amine can be bathed in a cerium-containing cyanide-containing phase and/or a cerium-rich phase. Preferably, the organic amine is a first amine, a second amine or a third amine, in other words an organic amine knife comprises a 3-amine functional group, a second amine functional group, or a third amine functional group. It should be understood here that the first amine functional group is a monosubstituted amine functional group covalently bonded to one carbon atom, and the second (four) energy group is a disubstituted amine functional group covalently bonded to two carbon atoms. The base, as well as the third amine functional group, are trisubstituted amines covalently bonded to three carbon atoms. Substituents covalently bonded to the amine functional group can be linear, branched, saturated or unsaturated, and/or contain a ring structure. Substituents covalently bonded to the amine functional group suitably comprise one or more heteroatoms. Here __ atoms are atoms that are not carbon or are not hydrogen. Suitable organic amines which can be used in the process according to the invention include, for example, aliphatic amines and aromatic amines, combinations thereof and derivatives substituted by heteroatoms. Suitable organic amines also include heteroatom-substituted amines and cyclic amines or combinations thereof. It is understood herein that the aliphatic amines are amines comprising one or more aliphatic groups covalently bonded to an amine functional group. Suitable aliphatic amines are alkylamines, cycloalkylamines, and cycloalkylalkylamines. Examples of suitable alkylamines are butylamine and hexylamine; suitable cycloalkylamines are cyclohexylamine; suitable cycloalkylamine amines are bis(aminomercapto)cyclohexane. Examples of suitable first amines are mercaptoamine, ethylamine, propylamine, hydroxypropylamine, and cyclohexylamine; examples of suitable second amines are dinonylamine, diethylamine, and diethanolamine; And the appropriate specification of the patent application No. 95,148,938, which is incorporated herein by reference. It is to be understood here that the aromatic amines are amines comprising one or more aromatic groups bonded to an amine functional group. The aromatic amines may be aromatic substituted amines and aralkylamines. Suitable aralkylamines are benzylamine and dimethyldiamine; suitable aromatic substituted amines include aniline and amphetamine. Suitable hetero atom-substituted derivatives are the aforementioned hydroxyethylamines and heterocyclic substituted amines such as melamine, 6-phenyl-2 4,7-azetidinetriamine and 2-amino-5-phenyl -4(5H)-4oxazoline. An example of an amine which is suitably substituted with a hetero atom is 2-(2-6-diphenoxy)ethylamine hydrazine. Suitable cyclic amines include pyrrolidine 'Wittidine, 吲η, and combinations thereof. The organic amine used in the process according to the invention comprises an amine, a diamine, a diamine, and a polyamine and mixtures thereof. The diamine is suitably a first amine, a second amine, a third amine or a combination thereof. The triamines and polyamines preferably comprise a second amine functional group or a combination of a second amine functional group and one or more first amine functional groups and/or with a third amine functional group. Suitable diamines are butane, pentane diamine and hexamethylene diamine. Suitable polyamines are, for example, polyethylenediamine. Preferably, the organic amine comprises a diamine, and more preferably the diamine is selected from the group consisting of ruthenium-butanediamine, hydrazine, 5-pentanediamine, hydrazine, 6-hexanediamine, and mixtures thereof. The advantage is that such amines are extremely suitable for the manufacture of polyamines. It is also preferred that the organic amine comprises a compound having an equivalent weight per amine functional group of up to 100, preferably in the range of from 35 to 80, more preferably in the range of from 4 to 6 :: having a lower equivalent weight per amine functional group The advantage of heavy organic amines is that organic amines have better solubility in ammonia-containing or hydrazine-rich liquid phases. It is also preferred that the organic amine has a molecular weight of less than 2 Å. The advantage is that it is easier to separate the organic amine from the liquid phase by replacing the distillation with the invention specification of the patent application No. 95,148,938. The acid which may be present in the composition comprising the organic amine may be any one which may be converted into a salt or a cerium salt which is insoluble or immiscible or nearly so rich in the ammonia phase and/or rich in cerium. phase. Whether the acid is suitable for use in this project can be tested simply by making a concentrated salt of acid or salt in water, and adding ammonia. If a precipitate forms when ammonia is added, the acid is suitable. a lower concentration of concentrated liquid 4 can be maintained to form a precipitate, and, or to maintain formation / redundancy; the lower ammonia amount of the temple, the lower the concentration, the more suitable the acid. Preferably k comprises a mineral acid, an organic acid, or a combination thereof. Suitable inorganic H) comprises a compound selected from the group consisting of hydrochloric acid, sulfuric acid, acid, nitric acid, Wei, squaraine and mixtures thereof. Examples of the organic acid are _ class' including two M, a short bond and a long chain and a slow acid. Particularly suitable for the sub-quantity _ or short chain _ (C1_C4), the short citric acid comprises a group selected from the group consisting of niacin (C1), 6 acid (C2) and propionic acid (C3) and mixtures thereof. Good compound. Preferably, the rhodium comprises a mineral acid, and more preferably the mineral acid comprises sulfuric acid or acid breaker or a mixture thereof. The advantage of containing sulfuric acid or phosphoric acid in the acid is that the salt or the salt formed with sulfuric acid or acid can be reused as a nitrogen feed in the fermentation process for organic amines. 20 people are better, and the acid contains sulfuric acid or scaly acid. The most preferred acid contains sulfuric acid. The advantage of acid-containing sulphuric acid is that the sulphuric acid salt or sulphate salt will form sulphuric acid in accordance with the process of the present invention, and may again be used in the gas feedstock process. A composition comprising an organic amine and an acid, or comprising an organic amine salt and an acid is suitable as a solid or a liquid. 10 1374127 Patent Application Serial No. 95,148,938, the disclosure of which is incorporated herein by reference. The solid composition may further comprise organic

A component other than an amine salt. The organic amine or its salt can be present in the solid composition at a wide range of different concentrations. This range is based on the analogy of organic amines and 5 depending on the type of acid used in combination with the organic amine. Preferably, the organic amine and the acid are present in the total amount of the solid composition, and the total weight of the solid composition is 50-100 wt.%', preferably 70-100 wt.%, more preferably 90-100 wt.%, and The best range of 99-100 wt·%. 15

When the composition comprising an organic amine and an acid or a salt thereof is a solid, the ammonia or hydrazine added and contacted with the solid is suitably a gas or a liquid. When ammonia or a gas is added, the organic amine can be stripped from the solid to form a broad or liquid ammonia-rich or ruthenium-rich phase containing organic amines. When ammonia or hydrazine is a liquid, the amine can be extracted from the solid, thereby forming a liquid-rich ammonia-rich camera containing an organic amine. The organic amine content of the solid phase is gradually decreasing. In order to strengthen the contact between the solid and the crucible, the solid can be stirred. Cyanide or an ammonia liquid, preferably when the composition comprising an organic amine and an acid is a solid. The advantage is that the amount of ammonia required to separate the organic amine from the composition is small. The use of hydrazine 20 When the composition is a liquid, the composition is suitably an aqueous solution. It has a salt (4) and a broad _ concentration exists in the aqueous solution. This aromatic amine is determined by the type of organic amine used and by the combination of the organic amines. Suitable organic amines are present in a concentration relative to the aqueous solution (total of 1 wt.%, preferably at least 2 wt%, or even at least 5 ^. at least wt.%, 20 wt%, and most preferably at least 3〇) Advantages of higher concentration ^ 11 1374127 Patent No. 95148938, the specification of the invention is replaced by the present invention, and in order to further enhance the effect of the present invention, it is necessary to add to form a salt with acid or a salt of salt. The amount or amount of ammonia in the two-phase system is significantly reduced. Preferably, prior to step (i) of the process according to the invention, the aqueous solution is concentrated, thereby increasing the organic amine or its acid or salt. The aqueous solution may be used in any suitable form. The method of the project is concentrated, for example, by evaporation by evaporation or by reverse osmosis. Evaporation can be achieved, for example, by steaming. It is preferred to use reverse osmosis as a concentration method of the aqueous solution. The advantage of reverse osmosis is that the treatment procedure can be further It is carried out at a mild temperature. Therefore, reverse osmosis can be applied to products which are sensitive to the formation of by-products under steaming conditions, thereby reducing the formation of by-products. 1〇&amp; The amount of ammonia added to the aqueous solution must be sufficient to form Multi-phase system. The required addition amount is determined by the concentration of organic amine in the aqueous solution and the degree of acidity, the choice of ammonia or hydrazine, and the temperature, for example, etc. Similarly, ammonia or ploughing is slightly excessive or excessively large to ensure acidification. The salt or arganic acid is used to precipitate the chamber as much as possible. The amount of the multiphase system and the amount of the sulphate salt can be determined by a skilled person. The preferred embodiment of the method according to the present invention. In step (1), ammonia is added to the aqueous solution. The advantage of ammonia is that it is cheap and easy to obtain. Most importantly, ammonia is a useful nitrogen feed for the fermentation process. Ammonia can be used as a gas or a liquid, = the pressure can be maintained Extremely mild pressure. 20 The aqueous solution according to the method of the present invention is suitable for the process stream obtained from the preparation of organic amines. The organic amine can be produced by any method and is suitable for chemical methods. The preferred method for preparing organic amines is fermentation. &lt;' In a preferred embodiment of the invention, the aqueous solution is obtained from a process stream obtained by a fermentation process, and the aqueous solution comprises sulfuric acid and/or Wei as an acid, in the patent of No. 12, 1374, 127, pp. The present invention replaces this 101. 6. 22| Adding ammonia to form a two-phase system. The advantage of this embodiment is that the precipitate formed comprises sulfuric acid and/or ammonium sulphate, which is easily separated and reused according to the method of the present invention. As a nitrogen feed for the fermentation process. In another preferred embodiment of the invention, the 'aqueous solution is derived from the fermentation of 5 to prepare a diamine, preferably butanediamine, pentamethylenediamine and/or hexamethylenediamine. Process stream obtained by the process. In several embodiments of the invention, the 'organoamine-rich phase is in the liquid phase, and the φ-rich acid phase is in the solid phase. For the step (ii) of the process according to the invention, the solid phase and the liquid are separated. For the phase 10, any one suitable for separating the solid phase and the liquid phase may be applied. Suitable methods are, for example, filtration, deposition, and spray. Suitable separation methods for the solid phase and the liquid phase are described, for example, in Kirk Orthmer, Encyclopedia of Chemical Technology. A suitable deposition method is, for example, a method of applying centrifugation. In this method, a deposit of the supernatant is formed, and the supernatant can be removed, for example, by decantation. Preferably, the 15 deposition is carried out in a hydrocyclone. The preferred hydrocyclone is connected to the evaporation spring g for separating high volatile components and low volatile components, which are further separated in a high pressure steaming column and a low pressure distillation column. Preferably, the liquid phase and the solid phase are separated by a hydrocyclone. The advantage of this method is that it can be more easily performed in a continuous process. 2〇 In order to separate the organic amine from the liquid phase in the step (iii) of the process according to the invention, any method suitable for separating the compound from the liquid phase can be applied. Suitable methods are, for example, a steaming method, a deposition method, an extraction method, and combinations thereof. A suitable distillation method is, for example, a method of removing ammonia or hydrazine by distillation. This method is applied to an organic monoamine, which is distilled at room temperature and/or in ammonia or hydrazine. The temperature of the distillate is liquid. A suitable house method is, for example, a method of adding a solvent which is miscible with ammonia or tillage, but the solvent is a non-solvent of an organic amine. This method is suitable for the case where the organic amine is a solid material at room temperature. An advantage of the method in which the organic amine is a solid material in the chamber 5 is that, when a solvent is added, the organic amine is precipitated from the liquid phase, and then the solid can be separated from the liquid phase by ordinary means. A suitable extraction method is, for example, a method in which a solvent is added, which is immiscible with ammonia or hydrazine, but the solvent is a good solvent for an organic amine. 1) Preferred organic amines are separated from the liquid phase by a test, in which ammonia and/or hydrazine are removed by steaming. An advantage of this separation method is that no additional solvent or non-solvent is added. An additional advantage of the process is that it is easier to apply to a process in which the organic amine consists of a mixture of amines comprising a liquid amine which must be further separated and isolated. 15 ® This steaming hall is preferably carried out in a sorting steaming hall. The sorting steaming hall is suitable for one or more steps. In the multi-step sorting _, it is preferred that the 'low boiling fraction and the high boiling fraction are separated in the first step; then in the second step and optionally the additional step, the low boiling fraction and/or Gao Fo Teng selects 3 - step separation 'to thereby obtain higher purity components in the liquid phase. It is suitable for the use of steamed cranes and/or at elevated temperatures. An additional advantage of having a steaming house is that the ammonia or spell obtained from the steaming hall does not contain Π' and can be reused in step (1) of the method of the invention. The method according to the invention, such as by means of a steamed crane, is suitable for use in a plant apparatus as shown in Fig. 1, Fig. 2 or Fig. 3. 14 1374127 101. 6_22 Patent Application Serial No. 95,148,938, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety in the in the in Any method is isolated from the phase. Preferably, the organic amine is isolated by selection, condensation, distillation and condensing operations. 5 Figures 1, 2, and 3 each show a schematic layout of an apparatus apparatus suitable for carrying out the single-off method of the present invention, which is integrated into an organic amine process. Figure 1 shows a layout of a device suitable for use in carrying out the device according to the invention. The apparatus (1) of Fig. 1 comprises a membrane unit (2) which is provided with an inlet tube (4) and outlet tubes (6) and (8). The inlet pipe (4) is connected to a separator unit (10) which is provided with an outlet pipe (12) and is connected to the reactor (16) through a connection pipe (14). The outlet tube (8) is connected to the mixer (18). The Kunhe combiner is further provided with an inlet pipe (2 〇) and an outlet pipe (22). The outlet pipe (22) is connected to a hydrocyclone (24) provided with outlets (28) and 15 (26). The outlet (26) is connected to the evaporator unit (3〇). The evaporator unit (30) is provided with two outlet pipes (32) and (34) which are respectively connected to the low pressure distillation column (36) and the high pressure distillation column (38). The low pressure distillation column (36) is provided with two outlets, namely a bottom outlet tube (40) and a top outlet tube (42). The high pressure distillation column (38) is also provided with two outlets, a bottom outlet (44) and a top outlet (46). The top outlet (46) 20 can be connected to the inlet tube (20). One or more of the bottom outlet (44), the top outlet tube (42) outlet (28) and the outlet (6) may be connected to an inlet tube (48) connected to the reactor (16). In the illustration of Figure 1, the process stream containing the organic amine is conducted from the reactor (16) through the connecting pipe (14), the separator unit (1〇) and the inlet pipe (4). 15 1374127 No. 95148938 The patent application specification replaces this 101. 6. 22 to the membrane unit (2). By applying a reverse osmosis treatment to the membrane unit, water can be separated from the process stream, whereby the process stream can be concentrated. Water can be released from the outlet (6) and the connected process stream can be fed to the mixer (18) via the outlet (8). Ammonia and/or helium may be fed to the mixer (18) via an inlet pipe (20) and mixed with the concentration process stream to form a multiphase system comprising a liquid phase and a solid phase. The mixture is fed via an outlet tube (22) to a hydrocyclone (24) where the liquid phase and solid phase can be separated. The liquid phase can reach the evaporator unit (30) via an outlet tube (26). In the evaporator unit (30), the liquid phase can be separated into a low pressure boiling fraction and a high pressure boiling fraction. The low pressure Fo Teng selection is fed to the low pressure distillation column (36) via the outlet pipe (32), and the 10 two pressure boiling selection is fed to the high pressure distillation column (38) via the outlet pipe (34). In the column (36), ammonia or helium may be separated from other components in the low pressure boiling fraction, and may be returned to the mixer (18) via an outlet tube (42) as needed. In the high pressure distillation column (38), the organic amine can be separated from the other components of the high pressure boiling fraction and released via the outlet tube (46). 15 Optionally, the waste stream or secondary flow from the membrane unit (2), the hydrocyclone (24), the low pressure distillation column (36) and/or the high pressure distillation column (36) may be passed through the inlet as needed. The tube (48) is returned to the reactor (14). Figure 2 shows a schematic layout of a device suitable for carrying out the detachment process according to the invention, similar to the device of Figure 1, but the membrane unit (2) can be replaced by 20 (5 Torr) evaporation. At evaporator t, the process stream can be concentrated by distillation. Figure 3 shows a schematic layout of a device suitable for carrying out the detachment process according to the invention, similar to the device of Figure 1, but the membrane unit (2) can be replaced by a crystallization device (52). In the crystallizer, the organic amine can be isolated from the process stream in the form of a salt with an acid. In this case, the salt is fed to the mixer (18). 16 1374127 101.6.21 Patent Application Serial No. 95148938 The present invention is further described by the following examples and comparative experimental examples. Analytical method Sulfate ion (S042-) content was determined by ion chromatography on a low volume anion exchange column. 5 Ammonium ion (NH4+) content is determined by ion chromatography on a low-capacity cation exchange column. The amine content was determined using HPLC. The amine was derivatized by treating the amine-containing sample with NBD-vaporation prior to the assay and the sample was injected into the interior of the HPLC apparatus where the derivative was separated by chromatography and detected by fluorescence. 10 Gas-like content is determined by GC-HD using a non-polar column. Quantification is carried out by internal standard methods. The materials used were the following various amines: 1,2-diamino-based, indole, 4-aminobutyryl, 1,5-diaminopentane, 1,6-diaminohexane, and 1-amine. Butane. 15 Example 1 In a 1.5-liter pressure cooker, 353 g of aqueous hydrazine, 4-diaminobutane (67 wt.% in water) and then 712 g of aqueous hydrochloric acid (37 wt.% in water) were added to make 500. A solution of gram sulfuric acid I,4·2 in 565 grams of water. The solution was heated to 80 ° C at ambient temperature, and then a vacuum was applied to steam to remove water. A solid no 20 water salt was obtained. Analysis showed that the molar ratio of 1,4-diaminobutane to SO/ was close to 1. This salt is used in the next step. 550 grams of liquid was added to 495 grams of butane sulfate 1,4-diammonium salt in a continuous blend. The slurry was stirred for 1 hour. After the completion of the stirring, the solid particles settled to form a supernatant. The composition of the supernatant was analyzed as follows. 9.1 grams of liquid was sampled into 881 grams of water. The aqueous solution is analyzed, and the liquid sample contains 11.2 17 1374127 101. 6. 21 The patent specification of the patent application No. 95148938 replaces the wt.% l,4-diaminobutane, 88.4 wt.% ammonia and less than 〇·5 wt. % s〇42·. Μ-Diaminobutane: S042· Mo ratio is 324.4.

Example II In a 1.5-liter pressure cooker, 160 g of aqueous 1,4-diaminobutyric (67 5 wt.% in water), 322 g of aqueous sulfuric acid (37 wt.% in water) and 84 g of water were added. A solution of 226 grams of butane sulfate 1,4-diammonium and 340 grams of water. Take 45 grams of sample. Analysis showed that the concentrations of 1,4-diaminobutane, SO/-, and water in the samples were 20 wt.%, 21 wt.%, and 59 wt.%, respectively. The starting solution thus contained 41 wt.% butane 1,4-diammonium sulfate. Liquid pure ammonia was slowly added to the remaining aqueous solution (521 10 g). A solid is formed directly in the liquid pool, but the solid is dissolved by stirring. When 200 ml of ammonia (corresponding to about 120 g) was fed, the solid formed could not be dissolved again. When a total amount of 380 ml of ammonia (corresponding to about 230 g) was added, the agitation was stopped after the solid particles were settled. The analysis showed that the concentrations of 1,4-diaminobutane, S042·, hydrazine and water in the samples were 17.6 wt.%, 3.5 15 wt.%, 4 〇 wt.%, and 38.9 wt.%, respectively. The molar ratio of 1,4-diaminobutyring: 8042_ was found to be 5.5.

Comparative Experimental Example A In a 1.5-liter pressure cooker, 85 g of aqueous 1,4-diaminobutane (67 wt.% in water), 171 g of aqueous sulfuric acid (37 wt.% in water) and 344 g of water were added. A solution of 20 grams of 120 grams of butane M-diammonium sulfate and 480 grams of water was prepared. Take 33 grams of sample. Slowly add liquid pure ammonia to the remaining aqueous solution (567 grams). A solid is formed directly in the liquid pool, but the solid is dissolved by stirring. The agitator was stopped when a total of 350 ml of ammonia (corresponding to about 21 g) was added. A clear solution free of solids was obtained. Examples 1 to 2 and comparative experimental examples show that the lower the amount of water, the separation by sulfate. The invention is replaced by the specification of the patent application No. 95148938. The better the Ίί i,4-diaminobutane.

Example III In 1.5 liters of South Steel, 66 g of aqueous 1,6-diaminohexanone, 149 g of aqueous sulfuric acid (37 wt.% in water) and 87 g of water were added to make 121 g of sulfuric acid. A solution of alkane 1,6-diammonium and 181 grams of water. Take 31 grams of sample. Liquid pure ammonia was slowly added to the remaining aqueous solution (271 g). A solid is formed directly in the liquid pool, but the solid is dissolved by stirring. When 190 ml (about 114 g) of ammonia was added, the solid formed did not dissolve. Stirring was stopped when 260 ml (about 156 g) of ammonia was added, the solid settled, and the resulting liquid phase was sampled. The liquid phase analysis showed that the concentrations of 1,6-diaminocarbazone, S042, ammonia and water in the sample were n.8 wt.%, 4.4 wt.%, 35.0 wt.%, and 48.8 wt.%, respectively. The molar ratio of 1,6-diaminohexane:S042- was calculated to be 2·2.

Example IV In a 1.5-liter pressure cooker, 60 g of 1,2-diaminoethane, 265 g of aqueous sulfuric acid (37 wt. Q / in water) and 70 g of water were added to obtain 158 g of ethane sulfate, 2 - 2 Money and 237 grams of water solution. Slowly add liquid pure ammonia. The solid is formed directly in the liquid pool but can be dissolved by stirring. When 19 mM (about n4 g) of ammonia was added, the solid formed was no longer dissolved. When 26 cc (about 156 g) of gas was added, the mixing was stopped, the solid was settled, and the obtained liquid phase sample was taken out. The liquid phase analysis showed that the concentrations of bismuth, 2_diaminoethane, s〇42-, ammonia and water in the sample were 10,5 wt.%, 3.0 wt.%, and 39.0 wt·, respectively. /. And 47.5 wt.%. The molar ratio of 1,2-diaminoethane:s〇42· was calculated to be 5 6 .

Example V In a 1.5-liter pressure cooker, 146 g of hydrazine-aminobutane was added, 265 g of aqueous 1374127, and the specification of the patent application No. 95148938 replaced the 101.0.62 sulfuric acid (37 wt.% in water) and 199 g of water. A solution of 244 g of di(n-butyl sulphate) sulphate and 366 g of water was obtained. Take 15 grams of sample. Slowly add liquid pure ammonia. The solid is formed directly in the liquid pool but can be dissolved by stirring. When 180 ml (about 108 g) of ammonia was added, the solid formed no longer dissolved. When 404 ml of 5 (about 242 g) of ammonia was added, the stirring was stopped, the solid settled, and the resulting liquid phase sample was taken out. The liquid phase analysis showed that the concentrations of the aminobutane, S042·, ammonia and water in the sample were 17.4 wt.%, 2.6 wt.%, 33.3 wt.%, and 46.7 wt.%, respectively. 1-Aminobutane calcination: S042-mole; the ratio was calculated to be 17.3, and the molar ratio was 8.65 times more excellent than the molar ratio in the di(1-ammonium butane) sulfate.

10 Example VI In a 1.5-liter pressure cooker, add 68 g of 1,5-diaminopentane (cadaverine), 175 g of aqueous sulfuric acid (37 wt.% in water) and 136 g of water to obtain 133 g of pentyl sulfate. · 1,5-two and 246 grams of water solution. Slowly add liquid pure ammonia. The solid is formed directly in the liquid pool but can be dissolved by stirring. When 195 ml (about 15 117 g) of ammonia was added, the solid formed did not dissolve. When 480 ml (about 288 g) of ammonia was added, the stirring was stopped, the solid was settled, and the obtained liquid phase sample was taken out. The liquid phase analysis showed that the concentrations of 1,5-diaminopentane, S042-, ammonia and water in the sample were 8.7 wt.%, 0.8 wt.%, 50.4 wt.°/〇, and 40.1 wt. %. The molar ratio of L5-diaminopentane: s〇42· was calculated to be 10.2. 2〇

Comparative Example B In a 1.5-liter pressure cooker, 91 g of 1,5-diaminopentane (cadaverine), 175 g of aqueous sulfuric acid (37 wt.%) and 350 g of water were added to form 156 g of pentane gasification 1 , 5 - 2 recorded and 460 grams of water solution. The acidity was measured to pH=8. Add 1 gram of potassium hydroxide ingot to the solution. The acidity of the solution was again measured as 'PH' 1 shown in 20 1374127 101.6. 22 Patent Application No. 95148938. In the replacement of the solution, 666 g of gas was added (450 ml of ρ was obtained in a total amount of 995 ml. After stirring for 1 hour) There are two liquid phases, 575 ml of the upper liquid phase and 42 〇 ml of the lower liquid phase. The second liquid phase is sampled and analyzed. The upper liquid phase shows an aqueous phase containing 143 wt·% cadaverine, 0.4 wt.% chloroform and 10.1 wt·% ci-ion; the difference is mainly 5 water. The lower liquid phase shows an organic phase containing &lt;0.1 wt.% cadaverine, 94.0 wt.% chloroform and llppm Cl_; the difference is mainly water. The amine is still almost completely present in the aqueous solution containing the chlorine anion, and the pH is corrected with potassium hydroxide and extracted with chloroform, and the yield of the obtained cadaverine is not good. 10 [Simple description of the drawing] Fig. 1, Fig. 2, and Fig. 3 The figures each show a schematic layout of a device device integrated into an organic amine process suitable for carrying out the single-off method of the present invention. [Main component symbol description] 1...device 18...mixer 2...membrane unit 20···Inlet pipe 4...inlet pipe 22...outlet pipe 6...outlet, outlet pipe 24...hydraulic cyclone 8...outlet,outlet pipe 26...outlet pipe 10...separator unit 28...outlet 12...outlet pipe 3〇...evaporator unit 14...connecting pipe 32...outlet Tube 16_._reactor 34...outlet tube 21 1374127 101. 6. 22 Patent Application No. 95148938 Inventor Specification Replacement 48...Inlet Tube 50...Evaporator 52...Crystalizer 36...Low Pressure Steaming Column 38 .. .High pressure steam tube column 40.. bottom outlet tube 42.. top outlet tube 44... bottom outlet 46... top outlet 22

Claims (1)

, eight monuments less production day _ ....... .. - 10, the scope of application for patents: 1. A separation of the organic amine from a composition comprising an organic amine and an acid or a salt comprising the organic amine and an acid A method, characterized in that the method comprises the steps of: 5 (1) adding ammonia or hydrazine to the composition, thereby forming a multiphase system comprising an organic amine-rich phase and an acid-rich phase, (ii) a separation step (1) the resulting organic-rich amine phase and the acid-rich phase, and (iii) separating the organic amine from the organic-rich amine phase. 10. The method of claim 1, wherein the organic amine is a diamine. 3. The method of claim 2, wherein the diamine is butanediamine, pentamethylenediamine, and hexamethylenediamine or a mixture thereof. 4. The method of claim 1, wherein the acid comprises a mineral acid or a short chain carboxylic acid. The method of claim 1, wherein the acid comprises sulfuric acid or phosphoric acid or a mixture thereof. 6. The method of claim 1, wherein the composition is a solid, and the ammonia or hydrazine is a liquid. 7. The method of claim 1, wherein the composition is an aqueous solution. The method of claim 7, wherein the organic amine is present in the aqueous solution at a concentration of at least 1 wt.% relative to the total weight of the aqueous solution. 9. The method of claim 7, wherein the aqueous solution is concentrated prior to step (i). 10. The method of claim 7, wherein in the step (1), the ammonia addition 23 1374127 101. 6. 22 Patent Application No. 95148938 is incorporated herein by reference. 11. The method of claim 7, wherein the aqueous solution is obtained from a process stream obtained from an organic amine manufacturing process. 12. The method of claim 11, wherein the process stream is a process stream obtained from the fermentation 5 process. 13. The method of claim 1, wherein the organic-rich amine phase is a liquid phase, and the acid-rich phase is a solid phase, and the liquid phase is separated from the solid phase by a spray. 14. The method of claim 1, wherein in step (iii), the 10 amines are separated from the liquid phase by distillation, and optionally, the ammonia or hydrazine obtained by distillation is used again Step (i). twenty four